US5225159A - Deodorization of sewage sludge-derived oils - Google Patents
Deodorization of sewage sludge-derived oils Download PDFInfo
- Publication number
- US5225159A US5225159A US07/806,330 US80633091A US5225159A US 5225159 A US5225159 A US 5225159A US 80633091 A US80633091 A US 80633091A US 5225159 A US5225159 A US 5225159A
- Authority
- US
- United States
- Prior art keywords
- sewage sludge
- sub
- derived oil
- oil
- traces
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010801 sewage sludge Substances 0.000 title claims abstract description 43
- 239000003921 oil Substances 0.000 title description 57
- 238000004332 deodorization Methods 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010802 sludge Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000002475 indoles Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 229960002317 succinimide Drugs 0.000 claims description 3
- 150000003557 thiazoles Chemical class 0.000 claims description 3
- 150000003567 thiocyanates Chemical class 0.000 claims description 3
- 150000003585 thioureas Chemical class 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 56
- 238000011282 treatment Methods 0.000 description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000001256 steam distillation Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 241001125843 Trichiuridae Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/343—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/916—Odor, e.g. including control or abatement
Definitions
- This invention relates to the treatment of sewage sludge-derived oils for the significant abatement of odours to allow for acceptability of utilization.
- Sewage sludge-derived oil may be produced according to the teachings of Canadian Patent No. 1,225,062 issued Aug. 4th, 1987 to T. R. Bridle, contents of which being incorporated herein by reference.
- the teachings of such a patent may, however, be summarized as follows.
- a batch-type reaction system for the production of such sludge-derived oil described in the above-identified Canadian patent may be operated as follows: A single reactor provides both heating and reaction zones and consists of a PYREXTM tube. This was heated in a furnace, off-gases being condensed in a trapping system consisting of three flasks connected in series, using ice as the coolant. Non-condensable gases (NCG) were vented by pipe from the system to a furnace hood and were not collected. A typical run was conducted by charging 550 g of dried sludge (93-96% solids) into the reactor and deaerating with nitrogen while in the vertical position. The reactor volumetric packing for all runs was a nominal 50%.
- the reactor was then placed in the furnace, which was inclined by a support 10° to facilitate liquid transport. All the lines, traps, etc. were connected and the entire system purged with nitrogen (15 mL/s) for 20 to 30 minutes.
- the furnace was then switched on and brought up to operating temperature at a controlled rate, the control employing a thermocouple placed in the sludge bed and connected to thermocouple switch and readout. Once operating temperature had been reached, the nitrogen purge rate was reduced to 7 mL/s. When all visible signs of reaction, i.e., gas/oil flow, ceased the heat was switched off and the nitrogen purge rate increased to 15 mL/s for approximately 30 minutes.
- the system was dismantled and the char, oil and pyrolytic water collected and stored for analyses, oil/water separation being achieved using a separatory funnel.
- NCG non-condensable gas
- the sewage sludge-derived oil produced appears to be largely aliphatic with a moderate oxygen content but with nitrogen derived from proteins and fatty acid in the sewage sludge.
- the solid residue is 80% inorganic matter.
- the above-described sewage sludge-derived oils may have the following composition:
- sewage sludge-derived oils can be dehydrated by distillation.
- Portions of the nitrogenous groups appear to be amines and amides with some pyridinic and pyrrolic types.
- Portions of the oxygen-containing groups appear to be carboxylic and amide types.
- That patent provided a process for treating hydrocarbon oils in order to separate nitrogenous substances, as well as other contaminants.
- the process included the first step of contacting the oil in the presence of water with an acid gas which has an affinity for nitrogenous substances under specified conditions.
- the conditions included temperature in the range of about 20° to about 90° C., sufficient pressure and contacting with an immiscible phase, e.g. water, an immiscible solvent or mixtures thereof. This was effective to provide removal of nitrogen-containing compounds.
- the second step involved separating the immiscible phase containing nitrogen-containing compounds from the hydrocarbon oils. In this way, basic nitrogen-containing compounds were removed from mineral oil, e.g. shale oil, by extraction with an immiscible aqueous phase containing an acid gas, e.g. carbon dioxide. The effectiveness of the separation was proportional to the partial pressure of the gas.
- compositions suitable for treatment by the recited process were any nitrogen-containing compounds, particularly primary, secondary, and tertiary amines and heterocyclic compounds, e.g. pyrrole, pyridine, indole, quinoline, etc., and their derivatives.
- Nitro-based materials which could be treated by that invention included shale oil, petroleum, and liquid products from tar sands and coal and lignite liquefaction.
- compositions are a sewage sludge-derived oil nor are they the art-recognized equivalent thereof.
- the procedures taught are for the removal of nitrogenous compounds and not necessarily for the removal of odouriferous compounds therein.
- the principal object of the present invention is to provide a method for the odour abatement of sewage sludge-derived oils to improve their acceptability for commerical utilization.
- a method for the significant reduction of odour of sewage sludge-derived oil in order to render the oils more acceptable for commerical utilization in such applications as for beneficial additives to asphalt, by steps of (A) distilling the sewage sludge-derived oil to a temperature of about 150° C. to remove water and volatile organic compounds and (B) circulating a gas consisting essentially of carbon dioxide therethrough.
- the sewage sludge-derived oils have the general composition range, typical range, specific composition and individual components as described hereinbefore.
- the sewage sludge-derived oil has the following range elemental composition:
- Nitrogen about 3.4% to about 5.0%
- the sewage sludge-derived oil has the following elemental composition:
- the individual components is the sewage sludge-derived oil have the following analysis, by gas chromatography:
- Oil was obtained from the pyrolysis of sewage sludge. This sewage sludge-derived oil was then distilled to 150° C. to remove the water and volatile organic components. The remaining phase was then subjected to the following twenty-one treatments. The results were determined and was evaluated by a panel of seven persons. Critical comparisons of levels of odours were made and the results were averaged. The results are summarized below in Table 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method is provided for treating a sewage sludge-derived oil having a particular chemical composition, to reduce its odor. The method includes the first step of distilling the sewage sludge-derived oil to 150° C. to remove water and volatile organic components, and then the essential step of circulating a gas consisting essentially of carbon dioxide gas therethrough.
Description
(i) Field of the Invention
This invention relates to the treatment of sewage sludge-derived oils for the significant abatement of odours to allow for acceptability of utilization.
(ii) Description of the Prior Art
Sewage sludge-derived oil may be produced according to the teachings of Canadian Patent No. 1,225,062 issued Aug. 4th, 1987 to T. R. Bridle, contents of which being incorporated herein by reference. The teachings of such a patent may, however, be summarized as follows.
A batch-type reaction system for the production of such sludge-derived oil described in the above-identified Canadian patent may be operated as follows: A single reactor provides both heating and reaction zones and consists of a PYREX™ tube. This was heated in a furnace, off-gases being condensed in a trapping system consisting of three flasks connected in series, using ice as the coolant. Non-condensable gases (NCG) were vented by pipe from the system to a furnace hood and were not collected. A typical run was conducted by charging 550 g of dried sludge (93-96% solids) into the reactor and deaerating with nitrogen while in the vertical position. The reactor volumetric packing for all runs was a nominal 50%. The reactor was then placed in the furnace, which was inclined by a support 10° to facilitate liquid transport. All the lines, traps, etc. were connected and the entire system purged with nitrogen (15 mL/s) for 20 to 30 minutes. The furnace was then switched on and brought up to operating temperature at a controlled rate, the control employing a thermocouple placed in the sludge bed and connected to thermocouple switch and readout. Once operating temperature had been reached, the nitrogen purge rate was reduced to 7 mL/s. When all visible signs of reaction, i.e., gas/oil flow, ceased the heat was switched off and the nitrogen purge rate increased to 15 mL/s for approximately 30 minutes. The system was dismantled and the char, oil and pyrolytic water collected and stored for analyses, oil/water separation being achieved using a separatory funnel.
The operating conditions and results for a continuous-type reactor system are shown in Table 1 below, while typical elemental analyses of the resultant oils and chars are shown in Table 2 and a distribution analysis of aliphatic hydrocarbons found in an oil is shown in Table 3. The continuous reactor results are shown in Table 4. All the data in the tables is expressed on a total solids basis (not corrected for volatiles). The non-condensable gas (NCG) yield was calculated by difference. Analysis of the NCG, by gas chromatography (GC), indicated that it contained roughly 6% methane and 10% carbon monoxide with the remainder comprising mostly carbon dioxide and nitrogen. The calculated calorific value is approximately 2.0 MJ/kg of NCG.
Most of the test runs were conducted at optimum conditions defined as: optimum conversion temperature as determined by differential scanning calorimetry; linear increase of temperature with time to operating temperature at 10° C/minute; and continuous nitrogen purge. Runs 11, 12, 13, 22, 24 and 19 instead were conducted with one variable altered during each test, as indicated in Table 1.
TABLE 1
__________________________________________________________________________
TEST RUN CONDITIONS AND RESULTS
__________________________________________________________________________
OIL
OPERATING CONDITIONS CALORIC
SLUDGE TEMP OTHER YIELD VALUE VISCOSITY
RUN NO.
SAMPLE (°C.)
COMMENTS % MJ/kg CENTISTOKES
__________________________________________________________________________
1,20,29
C 400 Optimum 20.8 36.40 Solid
5-10 D 450 Optimum 21.1 37.43 31.1
14,15,16
B 450 Optimum 24.1 33.13 60.5
2 C 425 63% WAS 25.8 33.83 70.3
3 C 425 75% WAS 28.6 34.13 97.5
4 C 425 88% WAS 28.7 31.77 214.0
11,12,13
B 350 Low Temperature
12.8 33.32 Solid
22 C 450 High Temperature
22.3 38.87 Solid
23 C 400 No N.sub.2 purge during run
19.8 38.00 44.9
24 C 400 Ramp at 5 C./min.
16.3 37.92 Solid
19 C 400 10000 ppm Ni spike
20.9 33.98 63.4
31 C 400 Second reactor, empty
19.0 37.49 Solid
32 C 400 Second reactor, char
17.2 38.18 39.5
33 C 400 Second reactor, catalyst
19.0 37.49 31.0
__________________________________________________________________________
RESULTS CHAR RUN
NONCONDEN- PYROLYTIC
CALORIC
SABLES WATER THERMAL
YIELD VALUE YIELD YIELD EFFICIENCY
RUN NO.
% MJ/kg % % %
__________________________________________________________________________
1,20,29
59.5 9.86 11.6 8.1 81.9
5-10 52.5 10.68 13.2 13.1 77.7
14,15,16
53.7 10.08 13.3 8.8 83.2
2 57.1 11.35 12.2 4.9 87.2
3 56.7 11.63 10.1 4.6 90.8
4 54.6 10.65 8.9 7.8 82.4
11,12,13
65.6 12.00 10.3 11.2 79.3
22 54.6 9.39 12.1 11.0 80.4
23 59.1 10.51 12.2 8.9 80.1
24 62.7 11.24 10.3 10.7 76.9
19 60.8 NA 10.6 7.7 88.7
31 60.0 11.07 12.0 9.0 80.1
32 59.9 11.07 13.0 9.9 77.0
33 56.8 10.01 14.8 9.4 75.0
__________________________________________________________________________
NA = Not Available
*Solid defined as 214 centistokes
.sup.+ Measured at room temperature (20-25° C.) of Table 5
measurement at 38° C. (ASTM standard)
TABLE 2
__________________________________________________________________________
OIL AND CHAR ELEMENTAL ANALYSIS (%)
OIL CHAR
Run No.
C H N S O C H N S O
__________________________________________________________________________
20 78.00
10.10
3.99
0.75
6.18
25.45
1.97
2.79
1.39
11.90
9 78.74
10.17
3.45
0.41
6.37
26.02
1.61
3.01
1.16
12.70
15 77.39
9.70
4.95
0.83
6.90
24.53
1.22
2.84
0.74
9.26
22 77.92
10.20
3.99
0.61
6.51
22.53
1.34
2.54
1.52
12.54
23 78.00
10.30
3.42
0.74
7.00
23.83
1.70
2.59
1.44
11.55
24 77.91
10.44
3.87
0.74
6.48
24.76
1.85
2.83
1.33
12.37
19 79.07
10.06
4.66
0.53
7.07
23.36
1.56
2.76
1.48
13.25
31 76.92
10.15
4.11
0.65
6.89
26.53
2.13
2.80
1.31
11.94
32 79.76
10.25
4.19
0.56
5.84
25.97
1.98
2.80
1.34
11.63
33 79.30
10.41
3.49
0.34
5.84
24.22
1.62
2.74
1.50
11.35
__________________________________________________________________________
TABLE 3
______________________________________
ALIPHATIC HYDROCARBON DISTRIBUTION IN OIL
Compound
%
______________________________________
C.sub.10
8
C.sub.10-15
30
C.sub.15-16
6
C.sub.16-17
5
C.sub.17-19
10
C.sub.19-20
10
C.sub.20-21
10
C.sub.21
21
100
______________________________________
TABLE 4
__________________________________________________________________________
CONTINUOUS REACTOR RESULTS
__________________________________________________________________________
REACTOR CONDITIONS
Sludge
Solids Char OIL
Run Temp Fd Rt
Residence
Inv.
Gas Gas Yield
Cal.
No. (°)
(g/h)
Time (Min)
(g) Seal
Path (%) Value
Viscosity
__________________________________________________________________________
34 350 750 8 51 no mixed 18.53
27.88
160
flow
35 450 750 8 54 no mixed 29.71
31.12
flow
36 500 750 8 53 no mixed 28.16
34.01
flow
37 450 750 28 201 yes counter 24.10
35.53
current
38 450 750 8 56 no 1st zone 24.46
30.06
only
39 450 750 8 55 no co- 27.96
33.20
current
40 450 1000 8 70 yes counter 26.75
31.04
current
41 450 500 20 88 yes counter 23.74
35.00
current
__________________________________________________________________________
NOG
CHAR Phys.
Run Yield
Cal. Yield
Cal. Water Thermal
Char In
No. (%) Value (%) Value Yield
(%) Effic'y
SFR
__________________________________________________________________________
34 64.68
8.84 7.28
3.18 3.62 73.85
0.068
35 72 59.76 8.27
7.57 5.04
2.18 96.80
0.072
36 34 58.10 7.67
3.61 20.05
3.06 98.04
0.071
37 33 59.50 8.28
6.37 9.68
5.72 93.77
0.268
38 110 59.47 8.25
9.26 3.72
4.23 83.75
0.075
39 73 59.74 8.70
6.67 6.07
5.60 98.91
0.073
40 82 61.11 8.54
4.76 7.20
3.37 92.14
0.070
41 34 57.79 8.12
7.42 10.96
5.88 91.82
0.176
__________________________________________________________________________
Measured at 38° C. (ASTM standard) of Table 1 measurement at room
temperature
Conducted using sludge from source "C
The sewage sludge-derived oil produced appears to be largely aliphatic with a moderate oxygen content but with nitrogen derived from proteins and fatty acid in the sewage sludge. The solid residue is 80% inorganic matter.
The above-described sewage sludge-derived oils may have the following composition:
______________________________________
General Range Typical Range
______________________________________
Nitrogen:
about 2% to about 8%
about 3.4% to about 5%
Oxygen: about 3% to about 12%
about 5.8% to about 6.9%
Sulphur:
about 0.1% to about 4%
about 0.3% to about 0.8%
Hydrogen:
about 8% to about 11%
about 9.7% to about
10.4%
Carbon: about 86.9% to about
about 76.9% to about
65% 79.8%
______________________________________
These sewage sludge-derived oils can be dehydrated by distillation. Portions of the nitrogenous groups appear to be amines and amides with some pyridinic and pyrrolic types. Portions of the oxygen-containing groups appear to be carboxylic and amide types.
The following Table provides an identification of individual components of sewage sludge-derived oil (SDO) by Gas Chromatography (GC)mass Spectrograph (MS):
______________________________________
Approximate
Approximate
concentration
concentration
in dehydrated sewage
Components in Fraction
sludge-derived oil
______________________________________
Fraction 1
(boiling: up to 176° C.)
(4.6% of dehydrated sewage sludge-derived oil)
Low boiling aromatics
15.3% 0.7%
Pyridines 1.1% 0.05%
Total Alkanes 2.5% 0.12%
Indoles 1.7% 0.08%
Pyrroles 1.1% 0.05%
Thiocyanates traces (i.e. less than 0.05%)
Esters traces (i.e. less than 0.05%)
Fraction 2
(boiling range: 176°-260° C.)
(22.5% of dehydrated sewage sludge-derived oil)
Phenols 3.2% 0.7%
Pyrroles
Esters/acids
Succinimide (C.sub.5 H.sub.7 NO.sub.2)
Amides traces (i.e. less than 0.05%)
Thioureas traces (i.e. less than 0.05%)
Thiazoles traces (i.e. less than 0.05%)
Fraction 3
(boiling range: 260-400° C.)
(30.6% of dehydrated sewage sludge-derived oil)
C.sub.n H.sub.2n-1 NO
C.sub.n H.sub.2n-1 N.
______________________________________
It was found that, as the fractions get heavier, the identification of individual components becomes more difficult because of the complexity of the fraction.
The actual analysis of this SDO is
N: 6.77%
O: 11.21%
S: 0.74%
H: 9.75%
C: 71.53%
It has previously been found that the sewage sludge-derived oils have considerable potential as beneficial additives in asphalt. The use of sewage sludge-derived oil for asphalt pavement is disclosed in copending application Ser. Nos. 07/641,861, now abandonded, and 07/641,872, now abandoned, each filed 16 Jan. 1991. Unfortunately, these sewage sludge-derived oils are highly odourific and this would be a deterring factor for this attractive utilization outlet. Therefore, significant odour abatement of these oils would improve their commercial utility.
The reduction of odours of vegetable oils by circulating carbon dioxide through such oils during steam distillation has been achieved by others, in particular, by L. Hartman and Daniela Reimans as described in "Preparation of Medium Chain Glyceride, With Use of Physical Refining" in Fett Wissenshaft and Technologie 1989, 91 (81 p 324).
The patent literature also discloses procedure for removing undesirable materials from organic materials. For example, U.S. Pat. No. 3,977,972 patented Aug. 31, 1976, by H. P. Bloch, provided a method and apparatus for reclaiming contaminated liquid, e.g. seal oil. The procedure provided for the reduction of H2 S by bubbling gas through it, e.g. nitrogen or air.
U.S. Pat. No. 3,992,285 patented Nov. 16, 1976, by L. E. Hutchins, provided a process for the conversion of hydrocarbonaceus black oil. The patented process involved desulphurization using a steam-containing gas and a desulfurization catalyst.
U.S. Pat. No. 4,406,778 patented Sep. 27, 1983, by M. Borza et al, provided a spent oil recovery process. The patented process involved the extraction and removal of insolubles from the oil using a gas under supercritical conditions.
U.S. Pat. No. 4,522,707 patented Jun. 11, 1985, provided, by E. Kriegel et al, a method for processing used oil. The patented process involved the extraction of used spindle and neutral oils with a gas under supercritical conditions.
U.S. Pat. No. 4,518,489 patented May 21, 1985, by D. O. Hitzman, provided an oil treatment process.
That patent provided a process for treating hydrocarbon oils in order to separate nitrogenous substances, as well as other contaminants. The process included the first step of contacting the oil in the presence of water with an acid gas which has an affinity for nitrogenous substances under specified conditions. The conditions included temperature in the range of about 20° to about 90° C., sufficient pressure and contacting with an immiscible phase, e.g. water, an immiscible solvent or mixtures thereof. This was effective to provide removal of nitrogen-containing compounds. The second step involved separating the immiscible phase containing nitrogen-containing compounds from the hydrocarbon oils. In this way, basic nitrogen-containing compounds were removed from mineral oil, e.g. shale oil, by extraction with an immiscible aqueous phase containing an acid gas, e.g. carbon dioxide. The effectiveness of the separation was proportional to the partial pressure of the gas.
That patentee further taught that organic compositions suitable for treatment by the recited process were any nitrogen-containing compounds, particularly primary, secondary, and tertiary amines and heterocyclic compounds, e.g. pyrrole, pyridine, indole, quinoline, etc., and their derivatives. Oil-based materials which could be treated by that invention included shale oil, petroleum, and liquid products from tar sands and coal and lignite liquefaction.
In view of the above-described technology and patents, there is thus an ever present need for the treatment of various carbonaceous compositions to remove undesirable components therefrom. Many expedients, as above described, have been advanced to treat various oil fractions. Examples of such treatment include the purification of mineral oils and other carbon-containing materials containing undesirable contaminants; the extraction of mineral oils to remove therefrom nitrogen-containing compounds and other impurities by extraction; the use of a CO2 or other acidic gases as extractants for the removal of contaminants from various organic compositions containing same; and the treatment of oils and other organic compositions containing nitrogen-containing compounds and undesirable contaminants, to render the oils and/or the nitrogen-containing compounds more desirable.
However, none of the above-described compositions is a sewage sludge-derived oil nor are they the art-recognized equivalent thereof. Moreover, the procedures taught are for the removal of nitrogenous compounds and not necessarily for the removal of odouriferous compounds therein.
(i) Aims of the Invention
The principal object of the present invention is to provide a method for the odour abatement of sewage sludge-derived oils to improve their acceptability for commerical utilization.
(ii) Statement of Invention
A method is provided herein for the significant reduction of odour of sewage sludge-derived oil in order to render the oils more acceptable for commerical utilization in such applications as for beneficial additives to asphalt, by steps of (A) distilling the sewage sludge-derived oil to a temperature of about 150° C. to remove water and volatile organic compounds and (B) circulating a gas consisting essentially of carbon dioxide therethrough.
(iii) Other Features of the Invention
The sewage sludge-derived oils have the general composition range, typical range, specific composition and individual components as described hereinbefore.
Thus in one feature, the sewage sludge-derived oil has the following range elemental composition:
Nitrogen: about 3.4% to about 5.0%
Oxygen: about 5.8% to about 6.9%
Sulphur: about 0.3% to about 0.8%
Hydrogen: about 9.7% to about 10.4%
Carbon: about 76.9% to about 79.8%.
In another feature of the invention, the sewage sludge-derived oil has the following elemental composition:
Nitrogen: 6.77%
Oxygen: 11.21%
Sulphur: 0.74%
Hydrogen: 9.75%
Carbon: 71.53%
By a still further feature of the invention, the individual components is the sewage sludge-derived oil have the following analysis, by gas chromatography:
______________________________________
Approximate
Approximate
concentration
concentration
in dehydrated sewage
Components in Fraction
sludge-derived oil
______________________________________
Fraction 1
(boiling: up to 176° C.)
(4.6% of dehydrated sewage sludge-derived oil)
Low boiling aromatics
15.3% 0.7%
Pyridines 1.1% 0.05%
Total Alkanes 2.5% 0.12%
Indoles 1.7% 0.08%
Pyrroles 1.1% 0.05%
Thiocyanates traces (i.e. less than 0.05%)
Esters traces (i.e. less than 0.05%)
Fraction 2
(boiling range: 176°-260° C.)
(22.5% of dehydrated sewage sludge-derived oil)
Phenols 3.2% 0.7%
Pyrroles
Esters/acids
Succinimide (C.sub.5 H.sub.7 NO.sub.2)
Amides traces (i.e. less than 0.05%)
Thioureas traces (i.e. less than 0.05%)
Thiazoles traces (i.e. less than 0.05%)
Fraction 3
(boiling range: 260-400° C.)
(30.6% of dehydrated sewage sludge-derived oil)
C.sub.n H.sub.2n-1 NO
C.sub.n H.sub.2n-1 N.
______________________________________
Oil was obtained from the pyrolysis of sewage sludge. This sewage sludge-derived oil was then distilled to 150° C. to remove the water and volatile organic components. The remaining phase was then subjected to the following twenty-one treatments. The results were determined and was evaluated by a panel of seven persons. Critical comparisons of levels of odours were made and the results were averaged. The results are summarized below in Table 5.
TABLE 5
______________________________________
Treatment Results
______________________________________
1. None Poor
2. Steam Distillation Poor
3. CO.sub.2 gas circulation
Good
4. Steam Distillation + CO.sub.2 gas circulation
Good
5. Air circulation Poor
6. Nitrogen gas circulation
Poor
7. High Pressure CO.sub.2 (no stirring)
Poor
8. High Pressure CO.sub.2 (no stirring), 100° C.
Poor
9. Wash with aqueous H.sub.2 O.sub.2 (1%)
Fair
10. Wash with aqueous NaOCL (0.1N)
Fair
11. Wash with aqueous NaOCL (0.1N) and
Good
CO.sub.2 circulation
12. Wash with aqueous Na.sub.2 SO.sub.3 (0.1N)
Fair
13. Wash with aqueous Acetic acid (0.1N)
Poor
14. Wash with aqueous CaO (0.1N)
Poor
15. Wash with aqueous NaOH (0.1N)
Poor
16. Wash with aqueous NaHCO.sub.3 (0.1N)
Poor
17. Wash with aqueous FeCL.sub.3 (0.1N)
Poor
18. Activated Charcoal (5%) Poor
19. Strong Acid Ion Exchange Resin (5%)
Poor
20. Weak Acid Ion Exchange Resin (5%)
Poor
21. Strong Base Ion Exchange Resin (5%)
Poor
______________________________________
As can be seen from treatment #2, steam distillation had little effect on odour reduction. However, bubbling carbon dioxide CO2 through the SDO at ambient temperature was quite effective in reducing the odour as shown in treatment #3. Since steam distillation could be used in the production of SDO its combination with CO2 circulation was tested and was also successful in odour reduction.
The significant odour reduction cannot be achieved solely by the sweeping action of gases as can be seen by treatments #5 and #6 in which air and nitrogen were circulated though the SDO without success. Treatment of the SDO with static carbon dioxide was unsuccessful as shown by treatments #7 and #8 in which the SDO was treated with CO2 under pressure at both ambient and at 100° C.
Treatment with dilute aqueous oxidizing agents such as sodium hypochlorite (bleach) and hydrogen peroxide as shown in treatments #9 and #10 produced some odour reduction. However, when in combination with CO2 as shown in treatment #11, the odour reduction was enhanced.
Treatment with dilute aqueous sodium sulphite as shown in #2 also resulted in some odour reduction.
Treatment with dilute aqueous acids and bases resulted in no significant odour reduction. Thus as shown in treatments #13, #14, #15, and #16 with acetic acid, calcium oxide (lime), sodium hydroxide and sodium bicarbonate resulted in no significant improvement. Neither did an aqueous solution of iron chloride as shown in #17.
In all the treatment with aqueous solutions, the volumes of the solutions used were twice those of the SDO.
Treatments with 5% of activated charcoal #18, 5% strongly acidic, #19, and weakly acidic #20 ion exchange resins and with 5% strongly basic ion exchange resins #21 resulted in no significant odour reduction.
These results indicate that passing CO2 through sewage sludge-derived oils cause the odour to become more acceptable, as judged by the volunteer panel. Other treatments that used CO2 gas were also suitable. Only trace amounts of materials were removed from the sewage sludge-derived oil.
When the sewage sludge-derived oil was added to hot recycled asphalt pavement at approximately 0.3% the odour was very strong. When sewage sludge-derived oil, that has had CO2 passed through it, according to the process of the present invention, was added at approximately 0.3% to hot recycled asphalt pavement, the odour was significantly reduced. The beneficial effects on asphalt were also retained.
These examples demonstrate the effectiveness of passing CO2 through sewage sludge-derived oil to reduce the odour.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Consequently, such changes and modifications are properly, equitably, and "intended" to be, within the full range of equivalence of the following claims.
Claims (4)
1. A method for treating a sewage sludge-derived oil comprising the steps of:
(A) providing sewage sludge-derived oil having the following elemental composition:
Nitrogen: about 2% to about 8%
Oxygen: about 3% to about 12%
Sulphur: about 0.1% to about 4%
Hydrogen: about 8% to about 11%
Carbon: about 86.9% to about 65%;
(B) distilling said sewage sludge-derived oil to a temperature of about 150° C. to remove water and volatile organic compounds; and
(C) circulating a gas consisting essentially of carbon dioxide therethrough.
2. The method of claim 1 wherein said sewage sludge-derived oil has the following range of elemental composition:
Nitrogen: about 3.4% to about 5.0%
Oxygen: about 5.8% to about 6.9%
Sulphur: about 0.3% to about 0.8%
Hydrogen: about 9.7% to about 10.4%
Carbon: about 76.9% to about 79.8%.
3. The method of claim 1 wherein said sewage sludge-derived oil has the following elemental composition:
Nitrogen: 6.77%
Oxygen: 11.21%
Sulphur: 0.74%
Hydrogen: 9.75%
Carbon: 71.53%
4. The method of claim 1 wherein the individual components of said sewage sludge-derived oil having the following analysis, by gas chromatography:
______________________________________
Approximate
Approximate
concentration
concentration
in dehydrated sewage
Components in Fraction
sludge-derived oil
______________________________________
Fraction 1
(boiling: up to 176° C.)
(4.6% of dehydrated sewage sludge-derived oil)
Low boiling aromatics
15.3% 0.7%
Pyridines 1.1% 0.05%
Total Alkanes 2.5% 0.12%
Indoles 1.7% 0.08%
Pyrroles 1.1% 0.05%
Thiocyanates traces (i.e. less than 0.05%)
Esters traces (i.e. less than 0.05%)
Fraction 2
(boiling range: 176°-260° C.)
(22.5% of dehydrated sewage sludge-derived oil)
Phenols 3.2% 0.7%
Pyrroles
Esters/acids
Succinimide (C.sub.5 H.sub.7 NO.sub.2)
Amides traces (i.e. less than 0.05%)
Thioureas traces (i.e. less than 0.05%)
Thiazoles traces (i.e. less than 0.05%)
Fraction 3
(boiling range: 260-400° C.)
(30.6% of dehydrated sewage sludge-derived oil)
C.sub.n H.sub.2n-1 NO
C.sub.n H.sub.2n-1 N.
______________________________________
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/806,330 US5225159A (en) | 1991-12-13 | 1991-12-13 | Deodorization of sewage sludge-derived oils |
| CA002084440A CA2084440A1 (en) | 1991-12-13 | 1992-12-03 | Deodorization of sewage sludge-derived oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/806,330 US5225159A (en) | 1991-12-13 | 1991-12-13 | Deodorization of sewage sludge-derived oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5225159A true US5225159A (en) | 1993-07-06 |
Family
ID=25193814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/806,330 Expired - Lifetime US5225159A (en) | 1991-12-13 | 1991-12-13 | Deodorization of sewage sludge-derived oils |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5225159A (en) |
| CA (1) | CA2084440A1 (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB252327A (en) * | 1925-05-20 | 1927-09-02 | William Bose Dobbin Penniman | Oxidized products, processes of making same, and apparatus therefor |
| US1999041A (en) * | 1931-03-04 | 1935-04-23 | Anglo Persian Oil Company Ltd | Method of deodorizing a hydrocarbon liquid |
| CA506182A (en) * | 1954-09-28 | P. Dayton Herbert | Treatment of hydrocarbons | |
| GB939699A (en) * | 1960-03-18 | 1963-10-16 | Sun Oil Co | Removal of nitrogen compounds from mineral oils |
| CA700946A (en) * | 1964-12-29 | Shell Oil Company | Removal of surfactants from jet fuel | |
| US3977972A (en) * | 1975-04-02 | 1976-08-31 | Exxon Research And Engineering Company | Method and apparatus for reclaiming contaminated liquid |
| US3992285A (en) * | 1974-09-23 | 1976-11-16 | Universal Oil Products Company | Process for the conversion of hydrocarbonaceous black oil |
| US4406778A (en) * | 1981-07-07 | 1983-09-27 | Snamprogetti S.P.A. | Spent oil recovery process |
| US4518489A (en) * | 1981-09-22 | 1985-05-21 | Phillips Petroleum Company | Oil Treatment |
| US4522707A (en) * | 1978-11-22 | 1985-06-11 | Fried. Krupp Gesellschaft Mit Beschrankter Haftung | Method for processing used oil |
| CA1248902A (en) * | 1983-10-21 | 1989-01-17 | Maria L. Chirinos | Method for desalting crude oil |
-
1991
- 1991-12-13 US US07/806,330 patent/US5225159A/en not_active Expired - Lifetime
-
1992
- 1992-12-03 CA CA002084440A patent/CA2084440A1/en not_active Abandoned
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA506182A (en) * | 1954-09-28 | P. Dayton Herbert | Treatment of hydrocarbons | |
| CA700946A (en) * | 1964-12-29 | Shell Oil Company | Removal of surfactants from jet fuel | |
| GB252327A (en) * | 1925-05-20 | 1927-09-02 | William Bose Dobbin Penniman | Oxidized products, processes of making same, and apparatus therefor |
| US1999041A (en) * | 1931-03-04 | 1935-04-23 | Anglo Persian Oil Company Ltd | Method of deodorizing a hydrocarbon liquid |
| GB939699A (en) * | 1960-03-18 | 1963-10-16 | Sun Oil Co | Removal of nitrogen compounds from mineral oils |
| US3992285A (en) * | 1974-09-23 | 1976-11-16 | Universal Oil Products Company | Process for the conversion of hydrocarbonaceous black oil |
| US3977972A (en) * | 1975-04-02 | 1976-08-31 | Exxon Research And Engineering Company | Method and apparatus for reclaiming contaminated liquid |
| US4522707A (en) * | 1978-11-22 | 1985-06-11 | Fried. Krupp Gesellschaft Mit Beschrankter Haftung | Method for processing used oil |
| US4406778A (en) * | 1981-07-07 | 1983-09-27 | Snamprogetti S.P.A. | Spent oil recovery process |
| US4518489A (en) * | 1981-09-22 | 1985-05-21 | Phillips Petroleum Company | Oil Treatment |
| CA1248902A (en) * | 1983-10-21 | 1989-01-17 | Maria L. Chirinos | Method for desalting crude oil |
Non-Patent Citations (1)
| Title |
|---|
| L. Hartman and Daniela Reimann as described in Preparation of Medium Chain Triglycerides, With the Use of Physical Refining in Fett Wissenshaft and Technologie, 1989, 91 (81 p. 324). * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2084440A1 (en) | 1993-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4113615A (en) | Method for obtaining substantially complete removal of phenols from waste water | |
| US6036748A (en) | Black water flash and vapor recovery method | |
| US4105545A (en) | Process for removing cyanide-containing components from aqueous media | |
| US3716474A (en) | High pressure thermal treatment of waste oil-containing sludges | |
| CA1149303A (en) | Coal extraction process | |
| JPH05286869A (en) | Method for recovering organosulfur compound from liquid oil | |
| US4566965A (en) | Removal of nitrogen and sulfur from oil-shale | |
| US4264453A (en) | Reclamation of coking wastes | |
| SU1766265A3 (en) | Method of processing fluid products of low-temperature carbonization of hydrocarbon-containing raw material | |
| KR19980070079A (en) | Emulsification Method and Apparatus of Waste Plastic | |
| US2930753A (en) | Waste water processing system | |
| US4175929A (en) | Process for control of pollutants generated during coal gasification | |
| US4588418A (en) | Recycle of reclaimed water in partial oxidation process | |
| US5225159A (en) | Deodorization of sewage sludge-derived oils | |
| US2409234A (en) | Revivifying adsorptive material | |
| JP2784270B2 (en) | Tank residual oil waste recovery method | |
| US4861446A (en) | Treatment of gas liquor | |
| US4839021A (en) | Treatment of petroleum derived organic sludges and oil residues | |
| US3783128A (en) | Process for recovering forest product plant wastes | |
| US4431511A (en) | Enhanced removal of nitrogen and sulfur from oil-shale | |
| CA2389354A1 (en) | A process for recovering hydrocarbons from a carbon containing material | |
| Steger et al. | Drying and low temperature conversion—A process combination to treat sewage sludge obtained from oil refineries | |
| US3211643A (en) | Production of oil from solid carbonaceous materials | |
| JPS6328676B2 (en) | ||
| RU2061858C1 (en) | Method for increased oil extraction from strata |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| AS | Assignment |
Owner name: HER MAJESTY THE QUEEN IN RIGHT OF CANADA AS REPRES Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SAWATZKY, HENRY;GIDDINGS, TERRANCE;FARNAND, BRIAN ANTHONY;REEL/FRAME:006773/0014;SIGNING DATES FROM 19930604 TO 19930825 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |